JP2023067525A - Method for producing perfluoroalkyl group-containing aromatic compound - Google Patents
Method for producing perfluoroalkyl group-containing aromatic compound Download PDFInfo
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- JP2023067525A JP2023067525A JP2021178861A JP2021178861A JP2023067525A JP 2023067525 A JP2023067525 A JP 2023067525A JP 2021178861 A JP2021178861 A JP 2021178861A JP 2021178861 A JP2021178861 A JP 2021178861A JP 2023067525 A JP2023067525 A JP 2023067525A
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- 125000005010 perfluoroalkyl group Chemical group 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 150000001491 aromatic compounds Chemical class 0.000 title abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 174
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052801 chlorine Chemical group 0.000 claims abstract description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 239000010949 copper Substances 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 239000003446 ligand Substances 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 238000005530 etching Methods 0.000 claims description 20
- 229910010272 inorganic material Inorganic materials 0.000 claims description 17
- 239000011147 inorganic material Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- -1 nitrogen-containing organic compound Chemical class 0.000 claims description 13
- 229910052740 iodine Chemical group 0.000 claims description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 29
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- UNBDDZDKBWPHAX-UHFFFAOYSA-N n,n-di(propan-2-yl)formamide Chemical compound CC(C)N(C=O)C(C)C UNBDDZDKBWPHAX-UHFFFAOYSA-N 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 5
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 5
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 238000012916 structural analysis Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 150000003222 pyridines Chemical class 0.000 description 4
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 3
- XEKTVXADUPBFOA-UHFFFAOYSA-N 1-bromo-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(Br)C(F)=C1F XEKTVXADUPBFOA-UHFFFAOYSA-N 0.000 description 3
- FFOMEQIMPYKURW-UHFFFAOYSA-N 4-(trifluoromethyl)-2-[4-(trifluoromethyl)pyridin-2-yl]pyridine Chemical group FC(F)(F)C1=CC=NC(C=2N=CC=C(C=2)C(F)(F)F)=C1 FFOMEQIMPYKURW-UHFFFAOYSA-N 0.000 description 3
- IMEVSAIFJKKDAP-UHFFFAOYSA-N 4-methoxy-2-(4-methoxypyridin-2-yl)pyridine Chemical group COC1=CC=NC(C=2N=CC=C(OC)C=2)=C1 IMEVSAIFJKKDAP-UHFFFAOYSA-N 0.000 description 3
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical group CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 description 3
- ZHMXQYAUGQASQM-UHFFFAOYSA-N 5-(trifluoromethyl)-2-[5-(trifluoromethyl)pyridin-2-yl]pyridine Chemical group N1=CC(C(F)(F)F)=CC=C1C1=CC=C(C(F)(F)F)C=N1 ZHMXQYAUGQASQM-UHFFFAOYSA-N 0.000 description 3
- PTRATZCAGVBFIQ-UHFFFAOYSA-N Abametapir Chemical group N1=CC(C)=CC=C1C1=CC=C(C)C=N1 PTRATZCAGVBFIQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- HBWBVIDKBKOVEX-UHFFFAOYSA-N methyl 2-(4-methoxycarbonylpyridin-2-yl)pyridine-4-carboxylate Chemical group COC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(=O)OC)=C1 HBWBVIDKBKOVEX-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- QKZWXPLBVCKXNQ-UHFFFAOYSA-N (2-methoxyphenyl)-[2-[(2-methoxyphenyl)-phenylphosphanyl]ethyl]-phenylphosphane Chemical compound COC1=CC=CC=C1P(C=1C=CC=CC=1)CCP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1 QKZWXPLBVCKXNQ-UHFFFAOYSA-N 0.000 description 2
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- IUMFOUVCDJGKNS-UHFFFAOYSA-N 2-(4-cyanopyridin-2-yl)pyridine-4-carbonitrile Chemical group N#CC1=CC=NC(C=2N=CC=C(C=2)C#N)=C1 IUMFOUVCDJGKNS-UHFFFAOYSA-N 0.000 description 2
- TZCAQUDTJIDJCE-UHFFFAOYSA-N 2-(trifluoromethyl)-6-[6-(trifluoromethyl)pyridin-2-yl]pyridine Chemical group FC(F)(F)C1=CC=CC(C=2N=C(C=CC=2)C(F)(F)F)=N1 TZCAQUDTJIDJCE-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WHLQQRGHOPIIMQ-UHFFFAOYSA-N [2-(2-diphenylphosphanyl-6-methylphenyl)-3-methylphenyl]-diphenylphosphane Chemical group CC=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(C)=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 WHLQQRGHOPIIMQ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- GYKMEKRMASHMIH-UHFFFAOYSA-N (1-benzyl-4-diphenylphosphanylpyrrolidin-3-yl)-diphenylphosphane Chemical compound C=1C=CC=CC=1CN(C1)CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C1P(C=1C=CC=CC=1)C1=CC=CC=C1 GYKMEKRMASHMIH-UHFFFAOYSA-N 0.000 description 1
- NFRYVRNCDXULEX-UHFFFAOYSA-N (2-diphenylphosphanylphenyl)-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C(=CC=CC=1)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 NFRYVRNCDXULEX-UHFFFAOYSA-N 0.000 description 1
- CDJHPMXMJUCLPA-UHFFFAOYSA-N (3-diphenylphosphanyl-2-bicyclo[2.2.1]hept-5-enyl)-diphenylphosphane Chemical compound C1C2C=CC1C(P(C=1C=CC=CC=1)C=1C=CC=CC=1)C2P(C=1C=CC=CC=1)C1=CC=CC=C1 CDJHPMXMJUCLPA-UHFFFAOYSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- XYKZEZPREAUXDQ-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethylbenzene Chemical compound FC(F)(F)C(F)(F)C1=CC=CC=C1 XYKZEZPREAUXDQ-UHFFFAOYSA-N 0.000 description 1
- WCUPMUYJNRBENK-UHFFFAOYSA-N 1,2,3,4,5-pentachloro-6-(trichloromethyl)benzene Chemical compound ClC1=C(Cl)C(Cl)=C(C(Cl)(Cl)Cl)C(Cl)=C1Cl WCUPMUYJNRBENK-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- WGOBPPNNYVSJTE-UHFFFAOYSA-N 1-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)CP(C=1C=CC=CC=1)C1=CC=CC=C1 WGOBPPNNYVSJTE-UHFFFAOYSA-N 0.000 description 1
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 description 1
- HKOAFLAGUQUJQG-UHFFFAOYSA-N 2-pyrimidin-2-ylpyrimidine Chemical group N1=CC=CN=C1C1=NC=CC=N1 HKOAFLAGUQUJQG-UHFFFAOYSA-N 0.000 description 1
- FWXAUDSWDBGCMN-UHFFFAOYSA-N 3-diphenylphosphanylbutan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 FWXAUDSWDBGCMN-UHFFFAOYSA-N 0.000 description 1
- XZKIHKMTEMTJQX-UHFFFAOYSA-N 4-Nitrophenyl Phosphate Chemical compound OP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 XZKIHKMTEMTJQX-UHFFFAOYSA-N 0.000 description 1
- CTYPJIUQROQJBG-UHFFFAOYSA-N 4-diphenylphosphanylpentan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)CC(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 CTYPJIUQROQJBG-UHFFFAOYSA-N 0.000 description 1
- MZFPAWGWFDGCHP-UHFFFAOYSA-N 5-diphenylphosphanylpentyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 MZFPAWGWFDGCHP-UHFFFAOYSA-N 0.000 description 1
- VFYDQLUPXAVOIK-UHFFFAOYSA-N C1(=CC=CC=C1)P([C-]1C=CC=C1)C1=CC=CC=C1.[C-]1(C(=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1)C(CN)N.[Fe+2] Chemical compound C1(=CC=CC=C1)P([C-]1C=CC=C1)C1=CC=CC=C1.[C-]1(C(=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1)C(CN)N.[Fe+2] VFYDQLUPXAVOIK-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- RZZDRSHFIVOQAF-UHFFFAOYSA-N [4-(5-diphenylphosphanyl-1,3-benzodioxol-4-yl)-1,3-benzodioxol-5-yl]-diphenylphosphane Chemical compound C=12OCOC2=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C1=C2OCOC2=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RZZDRSHFIVOQAF-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PLZFHNWCKKPCMI-UHFFFAOYSA-N cadmium copper Chemical compound [Cu].[Cd] PLZFHNWCKKPCMI-UHFFFAOYSA-N 0.000 description 1
- FWXAUDSWDBGCMN-ZEQRLZLVSA-N chiraphos Chemical compound C=1C=CC=CC=1P([C@@H](C)[C@H](C)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 FWXAUDSWDBGCMN-ZEQRLZLVSA-N 0.000 description 1
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- BOUYBUIVMHNXQB-UHFFFAOYSA-N dicyclohexyl(2-dicyclohexylphosphanylethyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCP(C1CCCCC1)C1CCCCC1 BOUYBUIVMHNXQB-UHFFFAOYSA-N 0.000 description 1
- YDFQUNJANDYTEQ-UHFFFAOYSA-N dicyclohexyl-[1-(2-dicyclohexylphosphanyl-5,6,7,8-tetrahydronaphthalen-1-yl)-5,6,7,8-tetrahydronaphthalen-2-yl]phosphane Chemical group C1CCCCC1P(C=1C(=C2CCCCC2=CC=1)C=1C(=CC=C2CCCCC2=1)P(C1CCCCC1)C1CCCCC1)C1CCCCC1 YDFQUNJANDYTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- MWVXFEZPEPOQRE-UHFFFAOYSA-N ditert-butyl(2-ditert-butylphosphanylethyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CCP(C(C)(C)C)C(C)(C)C MWVXFEZPEPOQRE-UHFFFAOYSA-N 0.000 description 1
- FJILYPCZXWVDMD-UHFFFAOYSA-N ditert-butyl(3-ditert-butylphosphanylpropyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CCCP(C(C)(C)C)C(C)(C)C FJILYPCZXWVDMD-UHFFFAOYSA-N 0.000 description 1
- JURBTQKVGNFPRJ-UHFFFAOYSA-N ditert-butyl(methyl)phosphane Chemical compound CC(C)(C)P(C)C(C)(C)C JURBTQKVGNFPRJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VJYFKVYYMZPMAB-UHFFFAOYSA-N ethoprophos Chemical compound CCCSP(=O)(OCC)SCCC VJYFKVYYMZPMAB-UHFFFAOYSA-N 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- TYRRWPJYBCYJPG-UHFFFAOYSA-N n,n'-bis(diphenylphosphanyl)-n,n'-bis(1-phenylethyl)ethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(C)N(P(C=1C=CC=CC=1)C=1C=CC=CC=1)CCN(P(C=1C=CC=CC=1)C=1C=CC=CC=1)C(C)C1=CC=CC=C1 TYRRWPJYBCYJPG-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/02—Monocyclic aromatic halogenated hydrocarbons
- C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本開示は、パーフルオロアルキル基含有芳香族化合物の製造方法に関する。 TECHNICAL FIELD The present disclosure relates to a method for producing a perfluoroalkyl group-containing aromatic compound.
パーフルオロトルエンに代表され、次世代エッチングガス等として期待されるパーフルオロアルキル基含有芳香族化合物の製造方法としては、例えば、ピリジン溶媒、銅、CF3I及びヨードベンゼンを用いた方法が知られている(非特許文献1参照)。 As a method for producing a perfluoroalkyl group-containing aromatic compound, which is typified by perfluorotoluene and expected as a next-generation etching gas, for example, a method using a pyridine solvent, copper, CF 3 I, and iodobenzene is known. (see Non-Patent Document 1).
本開示は、パーフルオロアルキル基含有芳香族化合物を、効率よく製造する方法を提供することを目的とする。 An object of the present disclosure is to provide a method for efficiently producing a perfluoroalkyl group-containing aromatic compound.
本開示は、以下の構成を包含する。 The present disclosure includes the following configurations.
項1.一般式(1): Section 1. General formula (1):
[式中、R1、R2、R3、R4及びR5は同一又は異なって、水素原子又はフッ素原子を示す。ただし、R1、R2、R3、R4及びR5のうち少なくとも1つはフッ素原子を示す。R6はパーフルオロアルキル基を示す。]
で表される化合物の製造方法であって、
(II)溶媒中で、
一般式(3):
R6Cu (3)
[式中、R6はパーフルオロアルキル基を示す。]
で表される化合物及び/又はその錯体と、一般式(2):
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and represent a hydrogen atom or a fluorine atom. However, at least one of R 1 , R 2 , R 3 , R 4 and R 5 represents a fluorine atom. R6 represents a perfluoroalkyl group. ]
A method for producing a compound represented by
(II) in a solvent,
General formula (3):
R6Cu (3)
[In the formula, R 6 represents a perfluoroalkyl group. ]
A compound and / or a complex thereof represented by the general formula (2):
[式中、R1、R2、R3、R4及びR5は前記に同じである。X1は臭素原子又は塩素原子を示す。]
で表される化合物とを反応させ、前記一般式(1)で表される化合物を生成させる工程(II)
を備える、製造方法。
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same as above. X 1 represents a bromine atom or a chlorine atom. ]
The step (II) of reacting with a compound represented by the general formula (1) to produce a compound represented by the general formula (1)
A manufacturing method comprising:
項2.前記工程(II)の前に、
(I)溶媒中で、
一般式(4):
R6X2 (4)
[式中、R6は前記に同じである。X2は臭素原子又はヨウ素原子を示す。]
で表される化合物と、銅を含む無機材料とを反応させ、前記一般式(3)で表される化合物及び/又はその錯体を生成させる工程(I)
を備える、項1に記載の製造方法。
Section 2. Before the step (II),
(I) in a solvent,
General formula (4):
R6X2 ( 4)
[In the formula, R 6 is the same as above. X2 represents a bromine atom or an iodine atom. ]
The step (I) of reacting a compound represented by and an inorganic material containing copper to produce a compound represented by the general formula (3) and/or a complex thereof
Item 1. The manufacturing method according to Item 1, comprising:
項3.前記R6の炭素数が1~5である、項1又は2に記載の製造方法。 Item 3. Item 3. The production method according to Item 1 or 2, wherein R 6 has 1 to 5 carbon atoms.
項4.前記R1、R2、R3、R4及びR5がいずれもフッ素原子である、項1~3のいずれか1項に記載の製造方法。 Section 4. 4. The production method according to any one of items 1 to 3, wherein all of R 1 , R 2 , R 3 , R 4 and R 5 are fluorine atoms.
項5.前記銅を含む無機材料が銅である、項1~4のいずれか1項に記載の製造方法。 Item 5. Item 5. The production method according to any one of Items 1 to 4, wherein the inorganic material containing copper is copper.
項6.前記溶媒が、窒素含有有機化合物である、項1~5のいずれか1項に記載の製造方法。 Item 6. Item 6. The production method according to any one of Items 1 to 5, wherein the solvent is a nitrogen-containing organic compound.
項7.前記工程(I)において、さらに、配位子化合物を添加する、項2~6のいずれか1項に記載の製造方法。 Item 7. Item 7. The production method according to any one of Items 2 to 6, wherein in the step (I), a ligand compound is further added.
項8.前記配位子化合物が、配位原子が窒素原子、リン原子、酸素原子又は硫黄原子である配位子化合物である、項7に記載の製造方法。 Item 8. Item 8. The production method according to Item 7, wherein the ligand compound is a ligand compound whose coordinating atom is a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom.
項9.前記工程(II)における反応温度が0~200℃である、項1~8のいずれか1項に記載の製造方法。 Item 9. Item 9. The production method according to any one of Items 1 to 8, wherein the reaction temperature in the step (II) is 0 to 200°C.
項10.一般式(1): Item 10. General formula (1):
[式中、R1、R2、R3、R4及びR5は同一又は異なって、水素原子又はフッ素原子を示す。ただし、R1、R2、R3、R4及びR5のうち少なくとも1つはフッ素原子を示す。R6はパーフルオロアルキル基を示す。]
で表される化合物と、
一般式(5):
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and represent a hydrogen atom or a fluorine atom. However, at least one of R 1 , R 2 , R 3 , R 4 and R 5 represents a fluorine atom. R6 represents a perfluoroalkyl group. ]
A compound represented by
General formula (5):
[式中、R1、R2、R3、R4及びR5は前記に同じである。]
で表される化合物、及び/又は一般式(6):
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same as above. ]
and / or a compound represented by the general formula (6):
[式中、R1、R2、R3、R4及びR5は前記に同じである。]
で表される化合物とを含有し、且つ、
組成物の総量を100モル%として、前記一般式(1)で表される化合物の含有量が10.0~99.9モル%である、組成物。
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same as above. ]
and a compound represented by
A composition in which the content of the compound represented by the general formula (1) is 10.0 to 99.9 mol% based on the total amount of the composition being 100 mol%.
項11.前記一般式(5)で表される化合物及び前記一般式(6)で表される化合物の合計含有量が、組成物の総量を100モル%として0.01~90.0モル%である、項10に記載の組成物。 Item 11. The total content of the compound represented by the general formula (5) and the compound represented by the general formula (6) is 0.01 to 90.0 mol% with respect to the total amount of the composition as 100 mol%. Item 11. The composition according to Item 10.
項12.クリーニングガス、エッチングガス、又は合成中間体として用いられる、項10又は11に記載の組成物。 Item 12. Item 12. The composition according to item 10 or 11, which is used as a cleaning gas, an etching gas, or a synthetic intermediate.
本開示によれば、パーフルオロアルキル基含有芳香族化合物を、効率よく製造する方法を提供することができる。 According to the present disclosure, it is possible to provide a method for efficiently producing a perfluoroalkyl group-containing aromatic compound.
本明細書において、「含有」は、「含む(comprise)」、「実質的にのみからなる(consist essentially of)」、及び「のみからなる(consist of)」のいずれも包含する概念である。 As used herein, "contain" is a concept that includes both "comprise," "consist essentially of," and "consist of."
また、本明細書において、数値範囲を「A~B」で示す場合、A以上B以下を意味する。 Further, in this specification, when a numerical range is indicated by "A to B", it means from A to B.
本開示において、「選択率」とは、反応器出口からの流出ガスにおける原料化合物以外の化合物の合計モル量に対する、当該流出ガスに含まれる目的化合物の合計モル量の割合(モル%)を意味する。 In the present disclosure, "selectivity" means the ratio (mol%) of the total molar amount of the target compound contained in the outflow gas to the total molar amount of compounds other than the raw material compounds in the outflow gas from the reactor outlet. do.
本開示において、「転化率」とは、反応器に供給される原料化合物のモル量に対する、反応器出口からの流出ガスに含まれる原料化合物以外の化合物の合計モル量の割合(モル%)を意味する。 In the present disclosure, the "conversion rate" refers to the ratio (mol%) of the total molar amount of compounds other than the raw material compound contained in the outflow gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor. means.
本開示において、「収率」とは、反応器に供給される原料化合物のモル量に対する、反応器出口からの流出ガスに含まれる目的化合物の合計モル量の割合(モル%)を意味する。 In the present disclosure, "yield" means the ratio (mol%) of the total molar amount of the target compound contained in the outflow gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.
1.パーフルオロアルキル基含有芳香族化合物の製造方法
本開示の製造方法は、
一般式(1):
1. Method for producing a perfluoroalkyl group-containing aromatic compound The production method of the present disclosure comprises:
General formula (1):
[式中、R1、R2、R3、R4及びR5は同一又は異なって、水素原子又はフッ素原子を示す。ただし、R1、R2、R3、R4及びR5のうち少なくとも1つはフッ素原子を示す。R6はパーフルオロアルキル基を示す。]
で表される化合物の製造方法であって、
(II)溶媒中で、
一般式(3):
R6Cu (3)
[式中、R6はパーフルオロアルキル基を示す。]
で表される化合物及び/又はその錯体と、一般式(2):
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and represent a hydrogen atom or a fluorine atom. However, at least one of R 1 , R 2 , R 3 , R 4 and R 5 represents a fluorine atom. R6 represents a perfluoroalkyl group. ]
A method for producing a compound represented by
(II) in a solvent,
General formula (3):
R6Cu (3)
[In the formula, R 6 represents a perfluoroalkyl group. ]
A compound and / or a complex thereof represented by the general formula (2):
[式中、R1、R2、R3、R4及びR5は前記に同じである。X1は臭素原子又は塩素原子を示す。]
で表される化合物とを反応させ、前記一般式(1)で表される化合物を生成させる工程(II)
を備える。
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same as above. X 1 represents a bromine atom or a chlorine atom. ]
The step (II) of reacting with a compound represented by the general formula (1) to produce a compound represented by the general formula (1)
Prepare.
また、本開示では、一般式(3)で表される化合物又はその錯体は、特に制限されるわけではないが、例えば、
(I)溶媒中で、
一般式(4):
R6X2 (4)
[式中、R6は前記に同じである。X2は臭素原子又はヨウ素原子を示す。]
で表される化合物と、銅を含む無機材料とを反応させ、前記一般式(3)で表される化合物及び/又はその錯体を生成させる工程(I)
により得ることが可能である。
Further, in the present disclosure, the compound represented by general formula (3) or a complex thereof is not particularly limited, but for example,
(I) in a solvent,
General formula (4):
R6X2 ( 4)
[In the formula, R 6 is the same as above. X2 represents a bromine atom or an iodine atom. ]
The step (I) of reacting a compound represented by and an inorganic material containing copper to produce a compound represented by the general formula (3) and/or a complex thereof
can be obtained by
パーフルオロトルエンに代表されるパーフルオロアルキル基含有芳香族化合物の製造方法としては、従来は、パークロロトルエンに代表されるパークロロアルキル基含有芳香族化合物を出発物質として、フッ化カリウムにより出発原料をフッ素化することが知られていた。 As a method for producing a perfluoroalkyl group-containing aromatic compound typified by perfluorotoluene, conventionally, a perchloroalkyl group-containing aromatic compound typified by perchlorotoluene is used as a starting material, and potassium fluoride is added as a starting material. was known to fluorinate.
しかしながら、上記の従来の方法では、反応温度を400~500℃と高温であるため、温和な条件で反応を進行させることが求められていた。 However, in the above-described conventional methods, the reaction temperature is as high as 400 to 500° C., so it has been required to proceed the reaction under mild conditions.
また、非特許文献1では、例えば、オートクレーブに、ピリジン溶媒、銅、CF3I及びヨードベンゼンを一括で投入して反応させることでパーフルオロトルエンを定量的に製造する方法が開示されている。しかしながら、この方法では、基質としてヨードベンゼンのように、ヨウ素原子を含む化合物を使用する必要があった。非特許文献1によれば、基質としてブロモベンゼンを用いた場合は、ペンタフルオロエチルベンゼンやベンゼン等の不純物が目的物と同程度生成することが示されており、パーフルオロトルエンを効率よく製造することはできなかった。このため、非特許文献1の方法は、基質の選択の幅に欠けるため、塩素原子、臭素原子等のような他のハロゲン原子を含む基質を使用して、パーフルオロアルキル基含有芳香族化合物を得る方法が求められていた。 Non-Patent Document 1 discloses, for example, a method for quantitatively producing perfluorotoluene by charging an autoclave with a pyridine solvent, copper, CF 3 I, and iodobenzene all at once and reacting them. However, this method required the use of a compound containing an iodine atom, such as iodobenzene, as a substrate. According to Non-Patent Document 1, when bromobenzene is used as a substrate, impurities such as pentafluoroethylbenzene and benzene are produced to the same extent as the target product, and perfluorotoluene can be efficiently produced. I couldn't. For this reason, the method of Non-Patent Document 1 lacks a wide range of substrate selection, so a substrate containing other halogen atoms such as a chlorine atom, a bromine atom, etc. is used to produce a perfluoroalkyl group-containing aromatic compound. I needed a way to get it.
本開示によれば、溶媒中で、パーフルオロアルキル基を含む銅化合物及び/又はその錯体と、基質である塩素原子又は臭素原子を含む芳香族化合物とを反応させることで、温和な条件で効率よく、パーフルオロアルキル基含有芳香族化合物を得ることができる。この際、反応温度をあまり高温としないことにより、得られるパーフルオロアルキル基含有芳香族化合物について高い選択率及び収率が得られる。なお、パーフルオロアルキル基を含む銅化合物及び/又はその錯体は、溶媒中で、パーフルオロアルキル基を含むヨウ素化合物と、銅を含む無機材料とを反応させることで得ることが可能である。 According to the present disclosure, a copper compound containing a perfluoroalkyl group and/or a complex thereof is reacted with an aromatic compound containing a chlorine atom or a bromine atom, which is a substrate, in a solvent. Often, a perfluoroalkyl group-containing aromatic compound can be obtained. At this time, by not setting the reaction temperature too high, high selectivity and yield of the obtained perfluoroalkyl group-containing aromatic compound can be obtained. A copper compound containing a perfluoroalkyl group and/or a complex thereof can be obtained by reacting an iodine compound containing a perfluoroalkyl group with an inorganic material containing copper in a solvent.
[1-1]工程(I)
本開示の製造方法において、工程(I)を採用する場合、溶媒中で、一般式(4)で表される化合物と、銅を含む無機材料とを反応させる。これにより、系中で一般式(3):
R6Cu (3)
[式中、R6はパーフルオロアルキル基を示す。]
で表される化合物及び/又はその錯体を形成することができる。
[1-1] Step (I)
In the manufacturing method of the present disclosure, when step (I) is employed, the compound represented by general formula (4) is reacted with an inorganic material containing copper in a solvent. This gives the general formula (3) in the system:
R6Cu (3)
[In the formula, R 6 represents a perfluoroalkyl group. ]
can form a compound represented by and/or a complex thereof.
具体的には、例えば、銅を含む無機材料として、銅を使用し、後述の配位子化合物を使用しない場合は、以下の反応式:
R6I + Cu → R6Cu + 1/2I2
[式中、R6は前記に同じである。]
にしたがって、パーフルオロアルキル基を含む銅化合物を得ることができる。
Specifically, for example, when copper is used as the copper-containing inorganic material and the ligand compound described below is not used, the following reaction formula:
R 6 I + Cu → R 6 Cu + 1/2I 2
[In the formula, R 6 is the same as above. ]
A copper compound containing a perfluoroalkyl group can be obtained according to.
(1-1-1)一般式(4)で表される化合物
一般式(4)で表される化合物は、一般式(4):
R6X2 (4)
[式中、R6はパーフルオロアルキル基を示す。X2は臭素原子又はヨウ素原子を示す。]
で表される化合物である。
(1-1-1) The compound represented by the general formula (4) The compound represented by the general formula (4) is represented by the general formula (4):
R6X2 ( 4)
[In the formula, R 6 represents a perfluoroalkyl group. X2 represents a bromine atom or an iodine atom. ]
It is a compound represented by
一般式(4)において、R6で示されるパーフルオロアルキル基は、全ての水素原子がフッ素原子で置換されたアルキル基を意味する。 In general formula (4), the perfluoroalkyl group represented by R6 means an alkyl group in which all hydrogen atoms are substituted with fluorine atoms.
パーフルオロアルキル基は、直鎖状、分岐鎖状及び環状のいずれも採用することができる。なかでも、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすい観点から、直鎖状パーフルオロアルキル基が好ましい。 Any of linear, branched and cyclic perfluoroalkyl groups can be employed. Among them, the compound represented by the general formula (3) and / or a complex thereof is likely to be formed in the step (I), the conversion rate of the step (II), the finally obtained general formula (1) A linear perfluoroalkyl group is preferable from the viewpoint of easily improving the yield, selectivity, and the like of the compound.
このパーフルオロアルキル基の炭素数は、特に制限されるわけではないが、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすい観点から、1~5が好ましく、1~4がより好ましく、1~3がさらに好ましい。 The number of carbon atoms in the perfluoroalkyl group is not particularly limited, but the compound represented by general formula (3) and/or its complex is likely to be formed in step (I), and the conversion in step (II) 1 to 5 are preferable, 1 to 4 are more preferable, and 1 to 3 are more preferable from the viewpoint of easily improving the yield, the selectivity, etc. of the compound represented by the general formula (1) finally obtained. .
このようなパーフルオロアルキル基としては、具体的には、トリフルオロメチル基、ペンタクルオロエチル基、ヘプタフルオロプロピル基等が挙げられる。 Specific examples of such perfluoroalkyl groups include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and the like.
一般式(4)において、X2は臭素原子又はヨウ素原子であり、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすい観点から、ヨウ素原子が好ましい。 In general formula (4), X 2 is a bromine atom or an iodine atom, the compound represented by general formula (3) and / or a complex thereof is likely to be formed in step (I), and the conversion rate in step (II) , an iodine atom is preferable from the viewpoint of easily improving the yield, selectivity, etc. of the finally obtained compound represented by the general formula (1).
上記のような条件を満たす一般式(4)で表される化合物としては、具体的には、CF3I、CF3Br、CF3CF2I、CF3CF2Br、CF3CF2CF2I、CF3CF2CF2Br等が挙げられる。 Specific examples of compounds represented by general formula (4) satisfying the above conditions include CF 3 I, CF 3 Br, CF 3 CF 2 I, CF 3 CF 2 Br, and CF 3 CF 2 CF. 2 I, CF 3 CF 2 CF 2 Br and the like.
上記の一般式(4)で表される化合物は、公知又は市販品を用いることができる。また、上記の一般式(4)で表される化合物は、単独で用いることもでき、2種以上を組合せて用いることもできる。 A known or commercially available product can be used as the compound represented by the general formula (4). Moreover, the compounds represented by the above general formula (4) can be used alone, or two or more of them can be used in combination.
(1-1-2)銅を含む無機材料
銅を含む無機材料としては、特に制限されないが、例えば、銅の他、ギルディング・メタル、丹銅、黄銅、リン青銅、ムンツメタル、アルミニウム青銅、ベリリウム銅、洋銅、白銅、カドニウム銅、クロム銅等の銅合金も挙げられる。なかでも、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすい観点から、銅が好ましい。
(1-1-2) Inorganic Materials Containing Copper Inorganic materials containing copper are not particularly limited. Copper alloys such as copper, western copper, cupronickel, cadmium copper, and chromium copper are also included. Among them, the compound represented by the general formula (3) and / or a complex thereof is likely to be formed in the step (I), the conversion rate of the step (II), the finally obtained general formula (1) Copper is preferable from the viewpoint of easily improving the yield, selectivity, and the like of the compound.
上記の銅を含む無機材料は、公知又は市販品を用いることができる。また、上記の銅を含む無機材料は、単独で用いることもでき、2種以上を組合せて用いることもできる。 As the inorganic material containing copper, known or commercially available products can be used. In addition, the above inorganic materials containing copper can be used alone, or two or more of them can be used in combination.
本開示の工程(I)において、銅を含む無機材料の使用量は、特に制限されないが、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすい観点から、一般式(4)で表される化合物1モルに対して、0.05~5.0モルが好ましく、0.1~3.0モルがより好ましく、0.2~2.0モルがさらに好ましい。 In step (I) of the present disclosure, the amount of the copper-containing inorganic material used is not particularly limited, but the compound represented by general formula (3) and / or a complex thereof is likely to be formed in step (I), and the step From the viewpoint of easily improving the conversion rate of (II), the yield of the finally obtained compound represented by the general formula (1), the selectivity, etc., per 1 mol of the compound represented by the general formula (4) is preferably 0.05 to 5.0 mol, more preferably 0.1 to 3.0 mol, even more preferably 0.2 to 2.0 mol.
(1-1-3)溶媒
工程(I)で使用できる溶媒としては、特に制限されないが、特に、一般式(4)で表される化合物、銅を含む無機材料等を溶解させる観点や、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすい観点から極性有機溶媒が好ましく、窒素含有極性溶媒がより好ましい。このような溶媒としては、例えば、アミド化合物(N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N,N-ジメチルアセトアミド、N,N-ジイソプロピルホルムアミド、N-メチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、1,3-ジメチル-3,4,5,6-テトラヒドロピリミジノン、ヘキサメチルリン酸トリアミド等)、アミン化合物(トリエチルアミン、1-メチルピロリジン等)、ピリジン化合物(ピリジン、メチルピリジン等)、キノリン化合物(キノリン、メチルキノリン等)等が挙げられる。なかでも、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、アミド化合物、ピリジン化合物等が好ましく、アミド化合物がより好ましく、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N,N-ジイソプロピルホルムアミド、N-メチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、1,3-ジメチル-3,4,5,6-テトラヒドロピリミジノン、ヘキサメチルリン酸トリアミド等がさらに好ましく、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N,N-ジイソプロピルホルムアミド、N-メチル-2-ピロリドン等が特に好ましく、N,N-ジメチルホルムアミド、N-メチル-2-ピロリドン等がさらに特に好ましい。
(1-1-3) Solvent The solvent that can be used in step (I) is not particularly limited. The compound represented by the general formula (3) and / or a complex thereof is likely to be formed by (I), the conversion rate of the step (II), the yield of the finally obtained compound represented by the general formula (1) A polar organic solvent is preferable, and a nitrogen-containing polar solvent is more preferable from the viewpoint of easily improving the selectivity. Examples of such solvents include amide compounds (N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric triamide, etc.), amine compounds (triethylamine, 1-methylpyrrolidine, etc.), pyridine compounds (pyridine, methylpyridine, etc.), quinoline compounds (quinoline, methylquinoline, etc.), and the like. Among them, the compound represented by the general formula (3) and / or a complex thereof is likely to be formed in the step (I), the conversion rate of the step (II), the finally obtained general formula (1) From the viewpoint of easily improving the yield, selectivity, etc. of the compound and easily reducing by-products, amide compounds, pyridine compounds and the like are preferable, and amide compounds are more preferable, N,N-dimethylformamide, N,N-diethyl. formamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethyl Phosphoric acid triamide and the like are more preferred, and N,N-dimethylformamide, N,N-diethylformamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone and the like are particularly preferred, and N,N-dimethylformamide, N- More particularly preferred are methyl-2-pyrrolidone and the like.
これらの溶媒は、公知又は市販品を使用することができる。また、これらの溶媒は、単独で用いることもでき、2種以上を組合せて用いることもできる。 Known or commercially available products can be used for these solvents. Moreover, these solvents can be used alone or in combination of two or more.
溶媒の使用量は、溶媒量であれば特に制限はなく、過剰量とすることができ、工程(I)により一般式(3)で表される化合物又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、一般式(4)で表される化合物100質量部に対して、80~10000質量部が好ましく、100~1000質量部がより好ましく、150~800質量部がさらに好ましい。 The amount of the solvent to be used is not particularly limited as long as it is the amount of the solvent, and it can be an excess amount. ), the yield of the compound represented by the finally obtained general formula (1), the selectivity, etc. are easily improved, and from the viewpoint of easy reduction of by-products, represented by the general formula (4) It is preferably 80 to 10000 parts by mass, more preferably 100 to 1000 parts by mass, and even more preferably 150 to 800 parts by mass with respect to 100 parts by mass of the compound.
(1-1-4)配位子化合物
本開示の工程(I)の反応は、さらに、配位子化合物の存在下に行うこともできる。特に、一般式(3)で表される化合物及び/又はその錯体の活性を上げることができる物質、つまり、銅に配位し得る配位子化合物を使用することが好ましい。
(1-1-4) Ligand compound The reaction of step (I) of the present disclosure can also be carried out in the presence of a ligand compound. In particular, it is preferable to use a substance capable of increasing the activity of the compound represented by the general formula (3) and/or its complex, that is, a ligand compound capable of coordinating to copper.
本開示の工程(I)の反応において、使用できる配位子化合物としては、例えば、配位原子が窒素原子、リン原子、酸素原子、硫黄原子等である配位子化合物が挙げられ、これらの配位子化合物には配位原子を1箇所のみ有する単座配位子と2箇所以上を有する多座配位子とがある。 Ligand compounds that can be used in the reaction of step (I) of the present disclosure include, for example, ligand compounds whose coordinating atoms are nitrogen atoms, phosphorus atoms, oxygen atoms, sulfur atoms, and the like. The ligand compounds include monodentate ligands having only one coordinating atom and multidentate ligands having two or more coordinating atoms.
単座配位子としては、例えば、トリフェニルホスフィン、トリメトキシホスフィン、トリエチルホスフィン、トリイソプロピルホスフィン、トリ(tert-ブチル)ホスフィン、トリ(n-ブチル)ホスフィン、トリイソプロポキシホスフィン、トリシクロペンチルホスフィン、トリシクロヘキシルホスフィン、ジ(tert-ブチル)メチルホスフィン、メチルジフェニルホスフィン、ジメチルフェニルホスフィン、トリエチルアミン、ピリジン等が挙げられる。 Monodentate ligands include, for example, triphenylphosphine, trimethoxyphosphine, triethylphosphine, triisopropylphosphine, tri(tert-butyl)phosphine, tri(n-butyl)phosphine, triisopropoxyphosphine, tricyclopentylphosphine, tri Cyclohexylphosphine, di(tert-butyl)methylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, triethylamine, pyridine and the like.
多座配位子としては、例えば、2,2’-ビピリジル、4,4’-(tert-ブチル)ビピリジル、4,4’-ビス(トリフルオロメチル)-2,2’-ビピリジル、5,5’-ビス(トリフルオロメチル)-2,2’-ビピリジル、6,6’-ビス(トリフルオロメチル)-2,2’-ビピリジル、4,4’-ビス(メトキシカルボニル)-2,2’-ビピリジル、4,4’-ジメチル-2,2’-ビピリジル、5,5’-ジメチル-2,2’-ビピリジル、4,4’-ジメトキシ-2,2’-ビピリジル、4,4’-ジシアノ-2,2’-ビピリジル、フェナントロリン、2,2’-ビピリミジル、1,4-ジアザビシクロ[2.2.2]オクタン、2-(ジメチルアミノ)エタノール、テトラメチルエチレンジアミン、N,N-ジメチルエチレンジアミン、N,N’-ジメチルエチレンジアミン、2-アミノメチルピリジン、1,1’-ビス(ジフェニルホスフィノ)フェロセン、ジフェニルホスフィノメタン、1,2-ビス(ジフェニルホスフィノ)エタン、1,3-ビス(ジフェニルホスフィノ)プロパン、1,5-ビス(ジフェニルホスフィノ)ペンタン、1,2-ビス(ジシクロヘキシルホスフィノ)エタン、1,3-(ジシクロヘキシルホスフィノ)プロパン、1,2-ビス(ジ-tert-ブチルホスフィノ)エタン、1,3-ビス(ジ-tert-ブチルホスフィノ)プロパン、1,2-ビス(ジフェニルホスフィノ)ベンゼン、1,5-シクロオクタジエン、2,2’-ビス(ジフェニルホスフィノ)-1,1’-ビナフチル(BINAP)、2,2’-ジメチル-6,6’-ビス(ジフェニルホスフィノ)ビフェニル(BIPHEMP)、1,2-ビス(ジフェニルホスフィノ)プロパン(PROPHOS)、2,3-O-イソプロピリデン-2,3-ジヒドロキシ-1,4-ビス(ジフェニルホスフィノ)ブタン(DIOP)、3,4-ビス(ジフェニルホスフィノ)-1-ベンジルピロリジン(DEGUPHOS)、1,2-ビス[(2-メトキシフェニル)フェニルホスフィノ]エタン(DIPAMP)、置換-1,2-ビスホスホラノベンゼン(DuPHOS)、5,6-ビス(ジフェニルホスフィノ)-2-ノルボルネン(NORPHOS)、N,N’-ビス(ジフェニルホスフィノ)-N,N’-ビス(1-フェニルエチル)エチレンジアミン(PNNP)、2,4-ビス(ジフェニルホスフィノ)ペンタン(SKEWPHOS)、1-[1’,2-ビス(ジフェニルホスフィノ)フェロセニル]エチレンジアミン(BPPFA)、2,2’-ビス(ジシクロヘキシルホスフィノ)-5,5’,6,6’,7,7’,8,8’-オクタヒドロ-1,1’-ビナフチル、((4,4’-ビ-1,3-ベンゾジオキソール)-5,5’-ジイル)ビス(ジフェニルホスフィン)(SEGPHOS)、2,3-ビス(ジフェニルホスフィノ)ブタン(CHIRAPHOS)、1-[2-(2置換ホスフィノ)フェロセニル]エチル-2置換ホスフィン(JOSIPHOS)等、及びこれらの混合物が挙げられる。上記BINAPとしては、BINAP(2,2’-ビス(ジフェニルホスフィノ)-1,1’-ビナフチル)の誘導体も含まれ、上記BIPHEMPとしては、BIPHEMP(2,2’-ジメチル-6,6’-ビス(ジフェニルホスフィノ)ビフェニル)の誘導体も含まれる。上記配位子化合物のうち、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、多座配位子が好ましく、2,2’-ビピリジル、4,4’-(tert-ブチル)ビピリジル、4,4’-ビス(トリフルオロメチル)-2,2’-ビピリジル、5,5’-ビス(トリフルオロメチル)-2,2’-ビピリジル、6,6’-ビス(トリフルオロメチル)-2,2’-ビピリジル、4,4’-ビス(メトキシカルボニル)-2,2’-ビピリジル、4,4’-ジメチル-2,2’-ビピリジル、5,5’-ジメチル-2,2’-ビピリジル、4,4’-ジメトキシ-2,2’-ビピリジル、4,4’-ジシアノ-2,2’-ビピリジル、フェナントロリン等がより好ましく、2,2’-ビピリジル、4,4’-ビス(トリフルオロメチル)-2,2’-ビピリジル、5,5’-ビス(トリフルオロメチル)-2,2’-ビピリジル、4,4’-ビス(メトキシカルボニル)-2,2’-ビピリジル、4,4’-ジメチル-2,2’-ビピリジル、5,5’-ジメチル-2,2’-ビピリジル、4,4’-ジメトキシ-2,2’-ビピリジル、フェナントロリンがさらに好ましい。 Polydentate ligands include, for example, 2,2′-bipyridyl, 4,4′-(tert-butyl)bipyridyl, 4,4′-bis(trifluoromethyl)-2,2′-bipyridyl, 5, 5'-bis(trifluoromethyl)-2,2'-bipyridyl, 6,6'-bis(trifluoromethyl)-2,2'-bipyridyl, 4,4'-bis(methoxycarbonyl)-2,2 '-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 5,5'-dimethyl-2,2'-bipyridyl, 4,4'-dimethoxy-2,2'-bipyridyl, 4,4' -dicyano-2,2'-bipyridyl, phenanthroline, 2,2'-bipyrimidyl, 1,4-diazabicyclo[2.2.2]octane, 2-(dimethylamino)ethanol, tetramethylethylenediamine, N,N-dimethyl ethylenediamine, N,N'-dimethylethylenediamine, 2-aminomethylpyridine, 1,1'-bis(diphenylphosphino)ferrocene, diphenylphosphinomethane, 1,2-bis(diphenylphosphino)ethane, 1,3- Bis(diphenylphosphino)propane, 1,5-bis(diphenylphosphino)pentane, 1,2-bis(dicyclohexylphosphino)ethane, 1,3-(dicyclohexylphosphino)propane, 1,2-bis(di -tert-butylphosphino)ethane, 1,3-bis(di-tert-butylphosphino)propane, 1,2-bis(diphenylphosphino)benzene, 1,5-cyclooctadiene, 2,2'- Bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 2,2'-dimethyl-6,6'-bis(diphenylphosphino)biphenyl (BIPHEMP), 1,2-bis(diphenylphosphino) Propane (PROPHOS), 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP), 3,4-bis(diphenylphosphino)-1-benzylpyrrolidine (DEGUPHOS), 1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane (DIPAMP), substituted-1,2-bisphosphoranobenzene (DuPHOS), 5,6-bis(diphenylphosphino)- 2-norbornene (NORPHOS), N,N'-bis(diphenylphosphino)-N,N'-bis(1-phenylethyl)ethylenediamine (PNNP), 2,4-bis(diphenylphosphino)pentane (SKEWPHOS) , 1-[1′,2-bis(diphenylphosphino)ferrocenyl]ethylenediamine (BPPFA), 2,2′-bis(dicyclohexylphosphino)-5,5′,6,6′,7,7′,8 ,8′-octahydro-1,1′-binaphthyl, ((4,4′-bi-1,3-benzodioxole)-5,5′-diyl)bis(diphenylphosphine) (SEGPHOS), 2, 3-bis(diphenylphosphino)butane (CHIRAPHOS), 1-[2-(disubstituted phosphino)ferrocenyl]ethyl-disubstituted phosphine (JOSIPHOS) and the like, and mixtures thereof. BINAP also includes derivatives of BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl), and BIPHEMP includes BIPHEMP (2,2'-dimethyl-6,6' -bis(diphenylphosphino)biphenyl) derivatives are also included. Among the above ligand compounds, the compound represented by the general formula (3) and / or a complex thereof is likely to be formed in the step (I), the conversion rate in the step (II), the finally obtained general formula (1 ) is easy to improve the yield, selectivity, etc. of the compound represented by, and from the viewpoint of easy reduction of by-products, polydentate ligands are preferred, 2,2'-bipyridyl, 4,4'-(tert -butyl)bipyridyl, 4,4'-bis(trifluoromethyl)-2,2'-bipyridyl, 5,5'-bis(trifluoromethyl)-2,2'-bipyridyl, 6,6'-bis( trifluoromethyl)-2,2'-bipyridyl, 4,4'-bis(methoxycarbonyl)-2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 5,5'-dimethyl -2,2'-bipyridyl, 4,4'-dimethoxy-2,2'-bipyridyl, 4,4'-dicyano-2,2'-bipyridyl, phenanthroline and the like are more preferable, and 2,2'-bipyridyl, 4 , 4′-bis(trifluoromethyl)-2,2′-bipyridyl, 5,5′-bis(trifluoromethyl)-2,2′-bipyridyl, 4,4′-bis(methoxycarbonyl)-2, 2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 5,5'-dimethyl-2,2'-bipyridyl, 4,4'-dimethoxy-2,2'-bipyridyl, phenanthroline are further preferable.
配位子化合物を使用する場合、その使用量は、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、銅を含む無機材料1モルに対して、通常、0.2~5.0モルが好ましく、0.3~3.0モルがより好ましく、0.5~2.0モルがさらに好ましい。 When using a ligand compound, the amount used is such that the compound represented by general formula (3) and / or a complex thereof is likely to be formed in step (I), the conversion rate in step (II), and finally From the viewpoint of easily improving the yield, selectivity, etc. of the compound represented by the obtained general formula (1) and easily reducing by-products, it is usually 0.2 per 1 mol of the inorganic material containing copper. ~5.0 mol is preferred, 0.3 to 3.0 mol is more preferred, and 0.5 to 2.0 mol is even more preferred.
(1-1-5)反応
本開示における工程(I)は、反応器中に原料を一括して仕込むバッチ式と、原料を反応器中に連続して供給しながら生成物を反応器から抜き出す連続式のいずれの方式でも採用できる。工程(I)の反応はそれほど速い反応ではないため、バッチ式を採用することが好ましい。
(1-1-5) Reaction Step (I) in the present disclosure is a batch type in which raw materials are charged into the reactor at once, and a product is extracted from the reactor while continuously supplying raw materials into the reactor. Any method of continuous type can be adopted. Since the reaction in step (I) is not a very fast reaction, it is preferable to employ a batch system.
(1-1-6)反応温度
本開示における工程(I)では、反応温度は、従来よりも温和な条件とすることができ、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、通常0~200℃が好ましく、5~150℃がより好ましく、10~80℃がさらに好ましい。
(1-1-6) Reaction temperature In step (I) in the present disclosure, the reaction temperature can be a milder condition than in the past, and step (I) is the compound represented by general formula (3) and / Or the complex is easily formed, the conversion rate of step (II), the yield of the finally obtained compound represented by general formula (1), the selectivity, etc. are easily improved, and by-products are reduced. From the viewpoint of ease of use, the temperature is generally preferably 0 to 200°C, more preferably 5 to 150°C, and even more preferably 10 to 80°C.
(1-1-7)反応時間
反応時間(最高到達温度における維持時間)は反応が十分に進行する程度とすることができ、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、1分~48時間が好ましく、5分~24時間がより好ましい。上記の反応時間は、バッチ式を採用する場合の好ましい反応時間であるが、連続式を採用する場合も反応時間は適宜調整することができ、その場合も副生成物を低減し易い観点から1分~48時間が好ましく、5分から24時間がより好ましい。
(1-1-7) Reaction time The reaction time (maintenance time at the highest temperature) can be set to the extent that the reaction proceeds sufficiently, and the compound represented by the general formula (3) and / Or its complex is easily formed, the conversion rate of step (II), the yield of the finally obtained compound represented by general formula (1), selectivity, etc. are easily improved, and by-products are easily reduced. From the point of view, the time is preferably 1 minute to 48 hours, more preferably 5 minutes to 24 hours. The above reaction time is a preferable reaction time when a batch system is employed, but the reaction time can be adjusted as appropriate when a continuous system is employed, and in that case also, from the viewpoint of facilitating the reduction of by-products. Minutes to 48 hours are preferred, and 5 minutes to 24 hours are more preferred.
(1-1-8)反応圧力
本開示における工程(I)の反応圧力は、工程(I)により一般式(3)で表される化合物及び/又はその錯体が形成されやすく、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、-2~2MPaが好ましく、-1~1MPaがより好ましく、-0.5~0.5MPaがさらに好ましい。なお、本開示において、圧力については特に表記が無い場合はゲージ圧とする。
(1-1-8) Reaction pressure The reaction pressure of step (I) in the present disclosure facilitates formation of the compound represented by general formula (3) and / or a complex thereof in step (I), and step (II) From the viewpoint of easily improving the conversion rate of the finally obtained compound represented by the general formula (1), selectivity, etc., and easily reducing by-products, -2 to 2 MPa is preferable, -1 ~1 MPa is more preferred, and -0.5 to 0.5 MPa is even more preferred. In addition, in the present disclosure, pressure is assumed to be gauge pressure unless otherwise specified.
本開示における工程(I)の反応において、一般式(4)で表される化合物と銅を含む無機材料とを反応させる反応器としては、上記温度及び圧力に耐え得るものであれば、形状及び構造は特に限定されない。反応器としては、例えば、縦型反応器、横型反応器、多管型反応器等が挙げられる。反応器の材質としては、例えば、ガラス、ステンレス、鉄、ニッケル、鉄ニッケル合金等が挙げられる。 In the reaction of step (I) in the present disclosure, the reactor for reacting the compound represented by the general formula (4) with the inorganic material containing copper should be able to withstand the above temperature and pressure. The structure is not particularly limited. Examples of reactors include vertical reactors, horizontal reactors, multitubular reactors, and the like. Examples of materials for the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloys.
(1-1-9)反応の例示
本開示における工程(I)を行う際の雰囲気については、一般式(4)で表される化合物と銅を含む無機材料との劣化を抑制する点から、不活性ガス雰囲気下が好ましい。
(1-1-9) Exemplification of reaction Regarding the atmosphere when performing step (I) in the present disclosure, from the viewpoint of suppressing deterioration of the compound represented by general formula (4) and the inorganic material containing copper, An inert gas atmosphere is preferred.
当該不活性ガスは、窒素、ヘリウム、アルゴン等が挙げられる。これらの不活性ガスのなかでも、コストを抑える観点から、窒素が好ましい。 Examples of the inert gas include nitrogen, helium, argon, and the like. Among these inert gases, nitrogen is preferable from the viewpoint of cost reduction.
反応終了後は、必要に応じて常法にしたがって精製処理を行い、一般式(3)で表される化合物及び/又はその錯体を得ることができる。また、精製を施さずに次の工程を行うこともできる。 After completion of the reaction, the compound represented by the general formula (3) and/or its complex can be obtained by performing a purification treatment according to a conventional method, if necessary. Alternatively, the next step can be performed without purification.
(1-1-10)目的化合物
このようにして工程(I)で生成される目的化合物は、一般式(3):
R6Cu (3)
[式中、R6はパーフルオロアルキル基を示す。]
で表される化合物及び/又はその錯体である。
(1-1-10) Target compound The target compound thus produced in step (I) has the general formula (3):
R6Cu (3)
[In the formula, R 6 represents a perfluoroalkyl group. ]
is a compound represented by and/or a complex thereof.
工程(I)において、配位子化合物を使用する場合は、一般式(3)で表される化合物に配位子化合物が配位した銅錯体が生成される。 When a ligand compound is used in step (I), a copper complex is produced in which the ligand compound is coordinated to the compound represented by the general formula (3).
例えば、配位子化合物として単座配位子又は二座配位子を使用する場合は、一般式(7A)又は(7B): For example, when using a monodentate ligand or a bidentate ligand as the ligand compound, general formula (7A) or (7B):
[式中、R6は前記に同じである。R7は上記の単座配位子を示す。R8は上記の二座配位子を示す。破線は配位結合を示す。]
で表される化合物が生成される。
[In the formula, R 6 is the same as above. R7 represents a monodentate ligand as described above. R8 represents a bidentate ligand as described above. Dashed lines indicate coordinate bonds. ]
A compound represented by is produced.
一般式(3)において、R6は前記したとおりである。 In general formula (3), R6 is as described above.
つまり、工程(I)で生成される目的化合物である一般式(3)で表される化合物は、具体的には、CF3Cu、CF3CF2Cu、CF3CF2CF2Cu等が挙げられる。 Specifically, the compound represented by the general formula (3), which is the target compound produced in step (I), is specifically CF 3 Cu, CF 3 CF 2 Cu, CF 3 CF 2 CF 2 Cu, or the like. mentioned.
一方、工程(I)で配位子化合物を使用する場合は、目的化合物は、例えば、 On the other hand, when using a ligand compound in step (I), the target compound is, for example,
等が挙げられる。 etc.
[1-2]工程(II)
本開示の製造方法において、工程(II)では、溶媒中で、一般式(3)で表される化合物及び/又はその錯体と、一般式(2)で表される化合物とを反応させて、一般式(1)で表される化合物を生成させる。
[1-2] Step (II)
In the production method of the present disclosure, in step (II), a compound represented by general formula (3) and/or a complex thereof and a compound represented by general formula (2) are reacted in a solvent, A compound represented by general formula (1) is produced.
(1-2-1)出発化合物(一般式(2))
本開示の工程(II)において使用できる出発化合物は、上記のとおり、一般式(2):
(1-2-1) starting compound (general formula (2))
Starting compounds that can be used in step (II) of the present disclosure are, as described above, of general formula (2):
[式中、R1、R2、R3、R4及びR5は同一又は異なって、水素原子又はフッ素原子を示す。ただし、R1、R2、R3、R4及びR5のうち少なくとも1つはフッ素原子を示す。X1は臭素原子又は塩素原子を示す。]
で表される化合物である。
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and represent a hydrogen atom or a fluorine atom. However, at least one of R 1 , R 2 , R 3 , R 4 and R 5 represents a fluorine atom. X 1 represents a bromine atom or a chlorine atom. ]
It is a compound represented by
一般式(2)において、R1、R2、R3、R4及びR5は、水素原子又はフッ素原子である。ただし、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、R1、R2、R3、R4及びR5のうち少なくとも1つはフッ素原子である。また、同様の理由により、R1、R2、R3、R4及びR5のうち少なくとも2つはフッ素原子であることが好ましく、R1、R2、R3、R4及びR5のうち少なくとも3つはフッ素原子であることがより好ましく、R1、R2、R3、R4及びR5のうち少なくとも4つはフッ素原子であることがさらに好ましく、R1、R2、R3、R4及びR5の全てがフッ素原子であることが特に好ましい。 In general formula (2), R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen atoms or fluorine atoms. However, from the viewpoint of easily improving the conversion rate of the step (II), the yield of the finally obtained compound represented by the general formula (1), the selectivity, etc., and easily reducing the by-product, R 1 , At least one of R2 , R3 , R4 and R5 is a fluorine atom. For the same reason, at least two of R 1 , R 2 , R 3 , R 4 and R 5 are preferably fluorine atoms, and R 1 , R 2 , R 3 , R 4 and R 5 At least three of them are more preferably fluorine atoms, and at least four of R 1 , R 2 , R 3 , R 4 and R 5 are more preferably fluorine atoms, and R 1 , R 2 , R It is particularly preferred that all of 3 , R4 and R5 are fluorine atoms.
一般式(2)において、X1は臭素原子又は塩素原子であり、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすい観点から、臭素原子が好ましい。 In the general formula (2), X 1 is a bromine atom or a chlorine atom, which improves the conversion rate of the step (II), the yield of the finally obtained compound represented by the general formula (1), the selectivity, etc. A bromine atom is preferred from the viewpoint of ease of
なお、一般式(2)において、Xがフッ素原子である場合は、工程(II)の反応は起こらない。 In general formula (2), when X is a fluorine atom, the reaction of step (II) does not occur.
また、一般式(2)において、Xがヨウ素原子である場合は、二量化反応が起こり、一般式(6): Further, in the general formula (2), when X is an iodine atom, a dimerization reaction occurs and the general formula (6):
[式中、R1、R2、R3、R4及びR5は前記に同じである。]
で表される化合物が生成されやすいために、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させることができず、効率的に反応を進行させることができない。
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same as above. ]
Because the compound represented by is likely to be produced, the yield, selectivity, etc. of the finally obtained compound represented by general formula (1) cannot be improved, and the reaction proceeds efficiently. can't
出発化合物である一般式(2)で表される化合物としては、具体的には、 Specific examples of the compound represented by the general formula (2), which is the starting compound, include:
等が挙げられる。 etc.
上記の一般式(2)で表される化合物は、公知又は市販品を用いることができる。また、上記の一般式(2)で表される化合物は、単独で用いることもでき、2種以上を組合せて用いることもできる。 A known or commercially available product can be used as the compound represented by the general formula (2). Moreover, the compounds represented by the general formula (2) can be used alone, or two or more of them can be used in combination.
(1-2-2)銅化合物及び/又はその錯体
なお、工程(II)で使用する一般式(3)で表される化合物及び/又はその錯体は、上記した工程(I)で得られたものを使用することもできるし、異なる製造方法により製造したものを使用することもできる。
(1-2-2) Copper compound and/or its complex The compound represented by the general formula (3) and/or its complex used in step (II) was obtained in step (I) above. It is also possible to use one manufactured by a different manufacturing method.
このため、使用できる一般式(3)で表される化合物及び/又はその錯体は、上記(1-1-10)で説明したものを使用することができる。 Therefore, the compound represented by the general formula (3) and/or its complex that can be used are those described in (1-1-10) above.
本開示の工程(II)において、一般式(3)で表される化合物及び/又はその錯体の使用量は、特に制限されないが、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすい観点から、一般式(2)で表される化合物1モルに対して、0.05~5.0モルが好ましく、0.1~3.0モルがより好ましく、0.2~2.0モルがさらに好ましい。 In step (II) of the present disclosure, the amount of the compound represented by general formula (3) and/or its complex used is not particularly limited, but the conversion rate of step (II), the finally obtained general formula ( From the viewpoint of easily improving the yield, selectivity, etc. of the compound represented by formula (1), it is preferably 0.05 to 5.0 mol, and 0.05 to 5.0 mol per 1 mol of the compound represented by general formula (2). 1 to 3.0 mol is more preferable, and 0.2 to 2.0 mol is even more preferable.
なお、上記の工程(I)に引き続いて、一般式(3)で表される化合物及び/又はその錯体を単離せずに工程(II)を行う場合は、上記と同様の理由により、一般式(2)で表される化合物1モルに対して、一般式(4)で表される化合物を0.05~5.0モル、好ましくは0.1~3.0モル、より好ましくは0.2~2.0モル使用し、銅を含む無機材料を0.05~5.0モル、好ましくは0.1~3.0モル、より好ましくは0.2~2.0モル使用することが好ましい。 In addition, following the above step (I), when performing the step (II) without isolating the compound represented by the general formula (3) and / or its complex, for the same reason as above, the general formula 0.05 to 5.0 mol, preferably 0.1 to 3.0 mol, more preferably 0.1 to 3.0 mol, more preferably 0.05 to 5.0 mol of the compound represented by general formula (4) per 1 mol of the compound represented by (2). 2 to 2.0 mol, and 0.05 to 5.0 mol, preferably 0.1 to 3.0 mol, more preferably 0.2 to 2.0 mol of an inorganic material containing copper. preferable.
(1-2-3)反応
本開示の工程(II)の反応では、一般式(3)で表される化合物を使用する場合、上記の一般式(2)で表される化合物、工程(I)で得られる一般式(3)で表される化合物とから、以下の反応式:
(1-2-3) Reaction In the reaction of step (II) of the present disclosure, when a compound represented by general formula (3) is used, the compound represented by general formula (2) above, step (I ) and the compound represented by the general formula (3) obtained in the following reaction scheme:
[式中、R1、R2、R3、R4、R5、R6及びXは前記に同じである。]
に従い、一般式(1)で表される化合物を得ることが好ましい。
[In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and X are the same as above. ]
It is preferable to obtain the compound represented by the general formula (1) according to.
(1-2-4)溶媒
工程(II)で使用できる溶媒としては、特に制限されないが、特に、一般式(2)で表される化合物、一般式(3)で表される化合物及び/又はその錯体等を溶解させる観点から極性有機溶媒が好ましい。また、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすい観点から窒素含有極性溶媒がより好ましい。このような溶媒としては、例えば、アミド化合物(N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N,N-ジメチルアセトアミド、N,N-ジイソプロピルホルムアミド、N-メチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、1,3-ジメチル-3,4,5,6-テトラヒドロピリミジノン、ヘキサメチルリン酸トリアミド等)、アミン化合物(トリエチルアミン、1-メチルピロリジン等)、ピリジン化合物(ピリジン、メチルピリジン等)、キノリン化合物(キノリン、メチルキノリン等)等が挙げられる。なかでも、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、アミド化合物、ピリジン化合物等が好ましく、アミド化合物がより好ましく、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N,N-ジイソプロピルホルムアミド、N-メチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、1,3-ジメチル-3,4,5,6-テトラヒドロピリミジノン、ヘキサメチルリン酸トリアミド等がさらに好ましく、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N,N-ジイソプロピルホルムアミド、N-メチル-2-ピロリドン等が特に好ましく、N,N-ジメチルホルムアミド、N-メチル-2-ピロリドン等がさらに特に好ましい。
(1-2-4) Solvent The solvent that can be used in step (II) is not particularly limited, but in particular, the compound represented by general formula (2), the compound represented by general formula (3) and / or A polar organic solvent is preferable from the viewpoint of dissolving the complex and the like. A nitrogen-containing polar solvent is more preferable from the viewpoint of easily improving the conversion rate in step (II), the yield of the finally obtained compound represented by the general formula (1), the selectivity, and the like. Examples of such solvents include amide compounds (N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric triamide, etc.), amine compounds (triethylamine, 1-methylpyrrolidine, etc.), pyridine compounds (pyridine, methylpyridine, etc.), quinoline compounds (quinoline, methylquinoline, etc.), and the like. Among them, from the viewpoint of easily improving the conversion rate in step (II), the yield and selectivity of the finally obtained compound represented by general formula (1), and easily reducing by-products, an amide compound is used. , pyridine compounds and the like are preferred, amide compounds are more preferred, and N,N-dimethylformamide, N,N-diethylformamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2- More preferred are imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric acid triamide, etc. N,N-dimethylformamide, N,N-diethylformamide, N,N -diisopropylformamide, N-methyl-2-pyrrolidone and the like are particularly preferred, and N,N-dimethylformamide, N-methyl-2-pyrrolidone and the like are more particularly preferred.
これらの溶媒は、公知又は市販品を使用することができる。また、これらの溶媒は、単独で用いることもでき、2種以上を組合せて用いることもできる。 Known or commercially available products can be used for these solvents. Moreover, these solvents can be used alone or in combination of two or more.
また、これらの溶媒は、工程(I)と同じ溶媒をそのまま使用することもできるし、工程(I)の溶媒とは別途、異なる溶媒を使用することもできる。 As these solvents, the same solvent as in step (I) can be used as it is, or a different solvent can be used separately from the solvent in step (I).
溶媒の使用量は、溶媒量であれば特に制限はなく、過剰量とすることができ、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、一般式(2)で表される化合物100質量部に対して、100~10000質量部が好ましく、200~1000質量部がより好ましく、300~800質量部がさらに好ましい。 The amount of solvent used is not particularly limited as long as it is the amount of solvent, and it can be an excess amount. , From the viewpoint of easily improving selectivity and the like and easily reducing by-products, 100 to 10000 parts by mass is preferable with respect to 100 parts by mass of the compound represented by the general formula (2), and 200 to 1000 parts by mass is More preferably 300 to 800 parts by mass.
(1-2-5)反応
本開示における工程(II)は、反応器中に原料を一括して仕込むバッチ式と、原料を反応器中に連続して供給しながら生成物を反応器から抜き出す連続式のいずれの方式でも採用できる。工程(II)の反応はそれほど速い反応ではないため、バッチ式を採用することが好ましい。
(1-2-5) Reaction Step (II) in the present disclosure is a batch method in which raw materials are charged into the reactor at once, and a product is extracted from the reactor while continuously supplying raw materials into the reactor. Any method of continuous type can be adopted. Since the reaction in step (II) is not a very fast reaction, it is preferable to adopt a batch system.
(1-2-6)反応温度
本開示における工程(II)では、反応温度は、従来よりも温和な条件とすることができ、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、通常0~200℃が好ましく、5~150℃がより好ましく、10~80℃がさらに好ましい。
(1-2-6) Reaction temperature In step (II) in the present disclosure, the reaction temperature can be a milder condition than conventional, the conversion rate of step (II), the finally obtained general formula ( From the viewpoint of easily improving the yield and selectivity of the compound represented by 1) and easily reducing by-products, the temperature is usually preferably 0 to 200°C, more preferably 5 to 150°C, and 10 to 80°C. More preferred.
(1-2-7)反応時間
反応時間(最高到達温度における維持時間)は反応が十分に進行する程度とすることができ、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、1分~48時間が好ましく、5分~24時間がより好ましい。上記の反応時間は、バッチ式を採用する場合の好ましい反応時間であるが、連続式を採用する場合も反応時間は適宜調整することができ、その場合も副生成物を低減し易い観点から1分~48時間が好ましく、5分から24時間がより好ましい。
(1-2-7) Reaction time The reaction time (maintenance time at the highest temperature) can be set to the extent that the reaction progresses sufficiently, the conversion rate of step (II), the finally obtained general formula (1 ) is preferably 1 minute to 48 hours, more preferably 5 minutes to 24 hours, from the viewpoint of easily improving the yield, selectivity, etc. of the compound represented by ) and easily reducing by-products. The above reaction time is a preferable reaction time when a batch system is employed, but the reaction time can be adjusted as appropriate when a continuous system is employed, and in that case also, from the viewpoint of facilitating the reduction of by-products. Minutes to 48 hours are preferred, and 5 minutes to 24 hours are more preferred.
(1-2-8)反応圧力
本開示における工程(II)の反応圧力は、工程(II)の転化率、最終的に得られる一般式(1)で表される化合物の収率、選択率等を向上させやすく、副生成物を低減しやすい観点から、-2~2MPaが好ましく、-1~1MPaがより好ましく、-0.5~0.5MPaがさらに好ましい。なお、本開示において、圧力については特に表記が無い場合はゲージ圧とする。
(1-2-8) Reaction pressure The reaction pressure of step (II) in the present disclosure is the conversion rate of step (II), the yield of the finally obtained compound represented by general formula (1), and the selectivity. etc., and from the viewpoint of easily reducing by-products, -2 to 2 MPa is preferable, -1 to 1 MPa is more preferable, and -0.5 to 0.5 MPa is even more preferable. In addition, in the present disclosure, pressure is assumed to be gauge pressure unless otherwise specified.
本開示における工程(II)の反応において、一般式(2)で表される化合物と一般式(3)で表される化合物及び/又はその錯体とを反応させる反応器としては、上記温度及び圧力に耐え得るものであれば、形状及び構造は特に限定されない。反応器としては、例えば、縦型反応器、横型反応器、多管型反応器等が挙げられる。反応器の材質としては、例えば、ガラス、ステンレス、鉄、ニッケル、鉄ニッケル合金等が挙げられる。なお、本開示における工程(II)は、上記した工程(I)で使用した反応器を用いることもできるし、上記した工程(I)で使用した反応器とは別途、異なる反応器を用いることもできる。 In the reaction of step (II) in the present disclosure, the reactor for reacting the compound represented by the general formula (2) with the compound represented by the general formula (3) and/or its complex has the above temperature and pressure The shape and structure are not particularly limited as long as they can withstand the pressure. Examples of reactors include vertical reactors, horizontal reactors, multitubular reactors, and the like. Examples of materials for the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloys. In addition, in step (II) in the present disclosure, the reactor used in step (I) described above can be used, or a different reactor can be used separately from the reactor used in step (I) described above. can also
(1-2-9)反応の例示
本開示における工程(II)は、工程(I)に引き続いて行うこともできるし、工程(I)とは別途行うこともできる。
(1-2-9) Exemplification of reaction Step (II) in the present disclosure can be carried out subsequently to step (I) or can be carried out separately from step (I).
本開示における工程(II)を行う際の雰囲気については、一般式(2)で表される化合物と一般式(3)で表される化合物及び/又はその錯体との劣化を抑制する点から、不活性ガス雰囲気下が好ましい。 Regarding the atmosphere when performing the step (II) in the present disclosure, from the viewpoint of suppressing deterioration of the compound represented by the general formula (2) and the compound represented by the general formula (3) and / or a complex thereof, An inert gas atmosphere is preferred.
当該不活性ガスは、窒素、ヘリウム、アルゴン等が挙げられる。これらの不活性ガスのなかでも、コストを抑える観点から、窒素が好ましい。 Examples of the inert gas include nitrogen, helium, argon, and the like. Among these inert gases, nitrogen is preferable from the viewpoint of cost reduction.
反応終了後は、必要に応じて常法にしたがって精製処理を行い、目的物である一般式(1)で表される化合物を得ることができる。 After completion of the reaction, purification treatment is performed according to a conventional method as necessary to obtain the target compound represented by the general formula (1).
(1-2-10)目的化合物
このようにして工程(II)で生成される目的化合物は、一般式(1):
(1-2-10) Target compound The target compound thus produced in step (II) has the general formula (1):
[式中、R1、R2、R3、R4、R5及びR6は前記に同じである。]
で表される化合物で表される化合物である。
[In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same as above. ]
It is a compound represented by a compound represented by.
一般式(1)において、R1、R2、R3、R4、R5及びR6は前記したとおりである。 In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as described above.
つまり、工程(II)で生成される目的化合物である一般式(1)で表される化合物は、具体的には、 That is, the compound represented by general formula (1), which is the target compound produced in step (II), is specifically:
等が挙げられる。 etc.
このようにして得られた一般式(1)で表される化合物は、半導体、液晶等の最先端の微細構造を形成するためのエッチングガス、クリーニングガス、合成中間体(有機合成用ビルディングブロック、例えばポリフルオロフェニル基導入のためのビルディングブロック等)等の各種用途に有効利用できる。有機合成用ビルディングブロックについては後述する。 The compound represented by the general formula (1) thus obtained is used as an etching gas, a cleaning gas, a synthetic intermediate (a building block for organic synthesis, a (for example, a building block for introducing a polyfluorophenyl group, etc.). Building blocks for organic synthesis are described below.
2.組成物
以上のようにして、一般式(1)で表される化合物を得ることができるが、一般式(1)で表される化合物と、一般式(5):
2. Composition As described above, the compound represented by the general formula (1) can be obtained, and the compound represented by the general formula (1) and the general formula (5):
[式中、R1、R2、R3、R4及びR5は前記に同じである。]
で表される化合物、及び/又は一般式(6):
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same as above. ]
and / or a compound represented by the general formula (6):
[式中、R1、R2、R3、R4及びR5は前記に同じである。]
で表される化合物とを含む組成物の形で得られることもある。
[In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are the same as above. ]
It may be obtained in the form of a composition containing the compound represented by.
一般式(5)において、R1、R2、R3、R4及びR5は前記したとおりである。上記したように、R1、R2、R3、R4及びR5のうち少なくとも1つはフッ素原子である。また、上記したように、R1、R2、R3、R4及びR5のうち少なくとも2つはフッ素原子であることが好ましく、R1、R2、R3、R4及びR5のうち少なくとも3つはフッ素原子であることがより好ましく、R1、R2、R3、R4及びR5のうち少なくとも4つはフッ素原子であることがさらに好ましく、R1、R2、R3、R4及びR5の全てがフッ素原子であることが特に好ましい。 In general formula (5), R 1 , R 2 , R 3 , R 4 and R 5 are as described above. As noted above, at least one of R 1 , R 2 , R 3 , R 4 and R 5 is a fluorine atom. Further, as described above, at least two of R 1 , R 2 , R 3 , R 4 and R 5 are preferably fluorine atoms, and R 1 , R 2 , R 3 , R 4 and R 5 At least three of them are more preferably fluorine atoms, and at least four of R 1 , R 2 , R 3 , R 4 and R 5 are more preferably fluorine atoms, and R 1 , R 2 , R It is particularly preferred that all of 3 , R4 and R5 are fluorine atoms.
つまり、一般式(5)で表される化合物は、具体的には、 Specifically, the compound represented by the general formula (5) is
等が挙げられる。 etc.
この場合、本開示の組成物においては、一般式(5)で表される化合物を少量含ませることで、アモルファスカーボン層(ACL)のエッチング速度と、シリコン酸化膜(SiO2)のエッチング速度との比(SiO2/ACL)をより大きくし、シリコン酸化膜(SiO2)をアモルファスカーボン層(ACL)と比較して選択的にエッチングしやすくすることが可能である。 In this case, in the composition of the present disclosure, by including a small amount of the compound represented by the general formula (5), the etching rate of the amorphous carbon layer (ACL) and the etching rate of the silicon oxide film (SiO 2 ) are improved. (SiO 2 /ACL) can be increased to make it easier to selectively etch the silicon oxide film (SiO 2 ) than the amorphous carbon layer (ACL).
このため、本開示の組成物の総量を100モル%として、一般式(1)で表される化合物の含有量は10.0~99.9モル%であり、20.0~99.9モル%、30.0~99.9モル%、40.0~99.9モル%、50.0~99.8モル%、60.0~99.7モル%、70.0~99.6モル%、80.0~99.4モル%等とすることも可能である。 Therefore, when the total amount of the composition of the present disclosure is 100 mol%, the content of the compound represented by general formula (1) is 10.0 to 99.9 mol%, and 20.0 to 99.9 mol. %, 30.0 to 99.9 mol%, 40.0 to 99.9 mol%, 50.0 to 99.8 mol%, 60.0 to 99.7 mol%, 70.0 to 99.6 mol %, 80.0 to 99.4 mol %, etc. are also possible.
また、本開示の組成物には、上記のとおり、出発物質である一般式(2)で表される化合物からハロゲン原子(塩素原子又は臭素原子)が脱離した一般式(5)で表される化合物も含まれ得る。この一般式(5)で表される化合物も、エッチングガス、クリーニングガス、合成中間体等として有用であるものの、一般式(5)で表される化合物を少量含ませることで、アモルファスカーボン層(ACL)のエッチング速度と、シリコン酸化膜(SiO2)のエッチング速度との比(SiO2/ACL)をより大きくし、シリコン酸化膜(SiO2)をアモルファスカーボン層(ACL)と比較して選択的にエッチングしやすくするために、一般式(5)で表される化合物の含有量は少量であることが好ましい。 In addition, as described above, the composition of the present disclosure includes a compound represented by general formula (5) in which a halogen atom (chlorine atom or bromine atom) is eliminated from the compound represented by general formula (2), which is a starting material. can also be included. Although the compound represented by the general formula (5) is also useful as an etching gas, a cleaning gas, a synthetic intermediate, etc., the amorphous carbon layer ( The ratio (SiO 2 /ACL) between the etching rate of the ACL) and the etching rate of the silicon oxide film (SiO 2 ) is increased, and the silicon oxide film (SiO 2 ) is selected in comparison with the amorphous carbon layer (ACL). It is preferable that the content of the compound represented by the general formula (5) is small in order to facilitate etching.
このため、本開示の組成物の総量を100モル%として、一般式(5)で表される化合物の含有量は0.1~90.0モル%が好ましく、0.1~80.0モル%、0.1~70.0モル%、0.1~60.0モル%、0.2~50.0モル%、0.3~40.0モル%、0.4~30.0モル%、0.6~20.0モル%、0.7~10.0モル%、0.8~5.0モル%等とすることも可能である。 Therefore, when the total amount of the composition of the present disclosure is 100 mol%, the content of the compound represented by general formula (5) is preferably 0.1 to 90.0 mol%, and 0.1 to 80.0 mol. %, 0.1 to 70.0 mol%, 0.1 to 60.0 mol%, 0.2 to 50.0 mol%, 0.3 to 40.0 mol%, 0.4 to 30.0 mol %, 0.6 to 20.0 mol %, 0.7 to 10.0 mol %, 0.8 to 5.0 mol %, etc. are also possible.
一般式(6)において、R1、R2、R3、R4及びR5は前記したとおりである。 In general formula (6), R 1 , R 2 , R 3 , R 4 and R 5 are as described above.
つまり、一般式(6)で表される化合物は、具体的には、 Specifically, the compound represented by the general formula (6) is
等が挙げられる。 etc.
この一般式(6)で表される化合物の含有量は、本開示の組成物の総量を100モル%として、70.0モル%以下が好ましく、40.0モル%以下がより好ましく、10.0モル%以下が特に好ましい。また、一般式(6)で表される化合物の含有量は、本開示の組成物の総量を100モル%として、0.1%以上であってよい。 The content of the compound represented by the general formula (6) is preferably 70.0 mol % or less, more preferably 40.0 mol % or less, based on 100 mol % of the total amount of the composition of the present disclosure. 0 mol % or less is particularly preferred. Moreover, the content of the compound represented by general formula (6) may be 0.1% or more based on 100 mol % of the total amount of the composition of the present disclosure.
また、上記した一般式(5)で表される化合物及び一般式(6)で表される化合物の合計含有量は、アモルファスカーボン層(ACL)のエッチング速度と、シリコン酸化膜(SiO2)のエッチング速度との比(SiO2/ACL)等の観点から、本開示の組成物の総量を100モル%として、0.1~90.0モル%であり、0.1~80.0モル%、0.1~70.0モル%、0.1~60.0モル%、0.2~50.0モル%、0.3~40.0モル%、0.4~30.0モル%、0.6~20.0モル%等とすることも可能である。 Further, the total content of the compound represented by the general formula (5) and the compound represented by the general formula (6) is the same as the etching rate of the amorphous carbon layer (ACL) and the etching rate of the silicon oxide film (SiO 2 ). From the viewpoint of the etching rate ratio (SiO 2 /ACL) and the like, the total amount of the composition of the present disclosure is 100 mol%, 0.1 to 90.0 mol%, 0.1 to 80.0 mol% , 0.1 to 70.0 mol%, 0.1 to 60.0 mol%, 0.2 to 50.0 mol%, 0.3 to 40.0 mol%, 0.4 to 30.0 mol% , 0.6 to 20.0 mol %.
このような本開示の組成物は、半導体、液晶等の最先端の微細構造を形成するためのエッチングガス、クリーニングガス、合成中間体(有機合成用ビルディングブロック、例えばポリフルオロフェニル基導入のためのビルディングブロック)等)等の各種用途に有効利用できる。有機合成用ビルディングブロック、クリーニングガス等の各種用途に有効利用できる。なお、有機合成用ビルディングブロックとは、反応性が高い骨格を有する化合物の前駆体となり得る物質を意味する。例えば、本開示の組成物とCF3Si(CH3)3等の含フッ素有機ケイ素化合物とを反応させると、CF3基等のパーフルオロアルキル基を導入して洗浄剤や含フッ素医薬中間体となり得る物質に変換することが可能である。 Such compositions of the present disclosure can be used as etching gases, cleaning gases, synthetic intermediates (building blocks for organic synthesis, for example, for introducing polyfluorophenyl groups) for forming cutting-edge fine structures such as semiconductors and liquid crystals. building blocks), etc.). It can be effectively used for various purposes such as building blocks for organic synthesis and cleaning gas. A building block for organic synthesis means a substance that can be a precursor of a compound having a highly reactive skeleton. For example, when the composition of the present disclosure is reacted with a fluorine-containing organosilicon compound such as CF 3 Si(CH 3 ) 3 , a perfluoroalkyl group such as a CF 3 group is introduced to produce detergents or fluorine-containing pharmaceutical intermediates. It is possible to convert to a substance that can be
以上、本開示の実施形態を説明したが、特許請求の範囲の趣旨及び範囲から逸脱することなく、形態や詳細の多様な変更が可能である。 Although the embodiments of the present disclosure have been described above, various changes in form and detail are possible without departing from the spirit and scope of the claims.
以下に実施例を示し、本開示の特徴を明確にする。本開示はこれら実施例に限定されるものではない。 Examples are provided below to clarify features of the present disclosure. The disclosure is not limited to these examples.
なお、本実施例では、特に断りのない限り、室温(25℃)で反応を行った。 In addition, in this example, the reaction was carried out at room temperature (25° C.) unless otherwise specified.
実施例1~5
オートクレーブに、溶媒(ピリジン、N-メチル-2-ピロリドン(NMP)又はN,N-ジメチルホルムアミド(DMF))10g、銅粉末0.71g(11mmol)を添加し蓋を閉めた。そこに、CF3I(2.2g,11mmol)を添加し、1時間撹拌した。
Examples 1-5
10 g of a solvent (pyridine, N-methyl-2-pyrrolidone (NMP) or N,N-dimethylformamide (DMF)) and 0.71 g (11 mmol) of copper powder were added to the autoclave and the lid was closed. CF 3 I (2.2 g, 11 mmol) was added thereto and stirred for 1 hour.
その後、反応液を19F-NMRにて分析すると、-26ppmにピークを確認した。FNMR_UWLU098378(Spectral Data were obtained from John Wiley & Sons, Inc.)と比較して、CF3Cuが生成していることを確認した。 After that, when the reaction solution was analyzed by 19 F-NMR, a peak was confirmed at -26 ppm. A comparison with FNMR_UWLU098378 (Spectral Data were obtained from John Wiley & Sons, Inc.) confirmed that CF 3 Cu was produced.
その後、オートクレーブにペンタフルオロフェニルブロミド(2.5g,10mmol)を添加して表1に示す温度で12時間撹拌し、反応を進行させた。 Then, pentafluorophenyl bromide (2.5 g, 10 mmol) was added to the autoclave and stirred at the temperature shown in Table 1 for 12 hours to allow the reaction to proceed.
反応終了後、ガスクロマトグラフィー、GCMS(ガスクロマトグラフィー質量分析法)にて質量分析を行い、NMR(核磁気共鳴)を用いて構造解析を行った。 After completion of the reaction, mass spectrometry was performed by gas chromatography and GCMS (gas chromatography mass spectrometry), and structural analysis was performed using NMR (nuclear magnetic resonance).
質量分析及び構造解析の結果から、目的物として From the results of mass spectrometry and structural analysis, the target product
が生成したことが確認できた。 was confirmed to have been generated.
実施例6
フェナントロリン(11mmol)を加えた以外は実施例1と同様に反応を進行させた。具体的には、以下のとおり反応を進行させた。
Example 6
The reaction was allowed to proceed as in Example 1, except that phenanthroline (11 mmol) was added. Specifically, the reaction was allowed to proceed as follows.
オートクレーブに、ピリジン10g、銅粉末0.71g(11mmol)、フェナントロリン(11mmol)を添加し蓋を閉めた。そこに、CF3I(2.2g,11mmol)を添加し、1時間撹拌した。実施例1~5と同様の方法で、系中で以下の化合物が生成したことを確認した。 10 g of pyridine, 0.71 g (11 mmol) of copper powder, and phenanthroline (11 mmol) were added to the autoclave and the lid was closed. CF 3 I (2.2 g, 11 mmol) was added thereto and stirred for 1 hour. By the same method as in Examples 1 to 5, it was confirmed that the following compounds were produced in the system.
その後、オートクレーブにペンタフルオロフェニルブロミド(2.5g,10mmol)を添加して表1に示す温度で12時間撹拌し、反応を進行させた。 Then, pentafluorophenyl bromide (2.5 g, 10 mmol) was added to the autoclave and stirred at the temperature shown in Table 1 for 12 hours to allow the reaction to proceed.
反応終了後、ガスクロマトグラフィー、GCMS(ガスクロマトグラフィー質量分析法)にて質量分析を行い、NMR(核磁気共鳴)を用いて構造解析を行った。 After completion of the reaction, mass spectrometry was performed by gas chromatography and GCMS (gas chromatography mass spectrometry), and structural analysis was performed using NMR (nuclear magnetic resonance).
比較例1
オートクレーブに、溶媒(ピリジン)10g、銅粉末0.71g(11mmol)、及びペンタフルオロフェニルブロミド(2.5g,10mmol)を添加し蓋を閉めた。そこに、CF3I(2.5g,13.2mmol)を添加して、50℃で12時間撹拌し、反応を進行させた。
Comparative example 1
10 g of solvent (pyridine), 0.71 g (11 mmol) of copper powder, and pentafluorophenyl bromide (2.5 g, 10 mmol) were added to the autoclave and the lid was closed. CF 3 I (2.5 g, 13.2 mmol) was added thereto and stirred at 50° C. for 12 hours to allow the reaction to proceed.
反応終了後、ガスクロマトグラフィー、GCMS(ガスクロマトグラフィー質量分析法)にて質量分析を行い、NMR(核磁気共鳴)を用いて構造解析を行った。 After completion of the reaction, mass spectrometry was performed by gas chromatography and GCMS (gas chromatography mass spectrometry), and structural analysis was performed using NMR (nuclear magnetic resonance).
質量分析及び構造解析の結果から、組成を確認した。 The composition was confirmed from the results of mass spectrometry and structural analysis.
結果を表1に示す。 Table 1 shows the results.
なお、表1において、C7F8、C6F5H、及びC12F10は、以下の化合物を意味する。 In addition , in Table 1 , C7F8 , C6F5H , and C12F10 mean the following compounds.
を示す。 indicates
実施例7
実施例1で得られた混合物を常法にて精製しC7F8(パーフルオロトルエン)を99モル%、C6F5H(ペンタフルオロベンゼン)を1モル%含む組成物を得た。これをICP(Inductive Coupled Plasma)、放電電力1000W、バイアス電力300W、圧力10mTorr、電子密度8×1010~2×1011cm-3、電子温度5~7eVのエッチング条件で、シリコン基板上に形成した1000μm厚さの酸化シリコン(SiO2)膜と、シリコン基板上に形成した5000μm厚さのアモルファスカーボン膜(ACL)のエッチング速度を測定し、その際のSiO2膜とACLとのエッチング速度の比(SiO2膜のエッチング速度/ACLのエッチング速度)を対ACL選択比とした。なお、SiO2膜は常法にしたがい形成し、ACLは既報(Producer(登録商標) APFTM PECVD - Applied Materials)に準拠して形成した。結果、対ACL選択比(SiO2膜のエッチング速度/ACLのエッチング速度)は3.2であった。
Example 7
The mixture obtained in Example 1 was purified by a conventional method to obtain a composition containing 99 mol % of C 7 F 8 (perfluorotoluene) and 1 mol % of C 6 F 5 H (pentafluorobenzene). This is formed on a silicon substrate under etching conditions of ICP (Inductive Coupled Plasma), discharge power of 1000 W, bias power of 300 W, pressure of 10 mTorr, electron density of 8×10 10 to 2×10 11 cm −3 , and electron temperature of 5 to 7 eV. A silicon oxide (SiO 2 ) film with a thickness of 1000 μm and an amorphous carbon film (ACL) with a thickness of 5000 μm formed on a silicon substrate were etched, and the etching rates were measured. (SiO 2 film etching rate/ACL etching rate) was taken as the selectivity ratio to ACL. The SiO 2 film was formed according to a conventional method, and the ACL was formed according to a previous report (Producer (registered trademark) APF™ PECVD—Applied Materials). As a result, the ACL selection ratio (SiO 2 film etching rate/ACL etching rate) was 3.2.
Claims (12)
で表される化合物の製造方法であって、
(II)溶媒中で、
一般式(3):
R6Cu (3)
[式中、R6はパーフルオロアルキル基を示す。]
で表される化合物及び/又はその錯体と、一般式(2):
で表される化合物とを反応させ、前記一般式(1)で表される化合物を生成させる工程(II)
を備える、製造方法。 General formula (1):
A method for producing a compound represented by
(II) in a solvent,
General formula (3):
R6Cu (3)
[In the formula, R 6 represents a perfluoroalkyl group. ]
A compound and / or a complex thereof represented by the general formula (2):
The step (II) of reacting with a compound represented by the general formula (1) to produce a compound represented by the general formula (1)
A manufacturing method comprising:
(I)溶媒中で、
一般式(4):
R6X2 (4)
[式中、R6は前記に同じである。X2は臭素原子又はヨウ素原子を示す。]
で表される化合物と、銅を含む無機材料とを反応させ、前記一般式(3)で表される化合物及び/又はその錯体を生成させる工程(I)
を備える、請求項1に記載の製造方法。 Before the step (II),
(I) in a solvent,
General formula (4):
R6X2 ( 4)
[In the formula, R 6 is the same as above. X2 represents a bromine atom or an iodine atom. ]
The step (I) of reacting a compound represented by and an inorganic material containing copper to produce a compound represented by the general formula (3) and/or a complex thereof
The manufacturing method of claim 1, comprising:
で表される化合物と、
一般式(5):
で表される化合物、及び/又は一般式(6):
で表される化合物とを含有し、且つ、
組成物の総量を100モル%として、前記一般式(1)で表される化合物の含有量が10.0~99.9モル%である、組成物。 General formula (1):
A compound represented by
General formula (5):
and / or a compound represented by the general formula (6):
and a compound represented by
A composition in which the content of the compound represented by the general formula (1) is 10.0 to 99.9 mol% relative to the total amount of the composition being 100 mol%.
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WO2012113726A1 (en) * | 2011-02-25 | 2012-08-30 | Fundació Privada Institut Català D'investigació Química (Iciq) | Process to obtain a trifluoromethylating composition |
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